CN111057215A - Polyurethane resin composition, fiber resin composite material, and preparation method and application thereof - Google Patents

Polyurethane resin composition, fiber resin composite material, and preparation method and application thereof Download PDF

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Publication number
CN111057215A
CN111057215A CN201811205127.1A CN201811205127A CN111057215A CN 111057215 A CN111057215 A CN 111057215A CN 201811205127 A CN201811205127 A CN 201811205127A CN 111057215 A CN111057215 A CN 111057215A
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polyol
isocyanate
parts
acrylate
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CN111057215B (en
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黄少华
周明
钱雄
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BYD Co Ltd
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BYD Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
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    • C08K7/00—Use of ingredients characterised by shape
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    • C08K7/04—Fibres or whiskers inorganic
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
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    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
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    • C08L2205/00—Polymer mixtures characterised by other features
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  • Polymers & Plastics (AREA)
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  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of polymer preparation, and discloses a polyurethane resin composition, a fiber resin composite material prepared from the polyurethane resin composition and application of the fiber resin composite material. The polyurethane resin composition comprises a component A and a component B, wherein the component A contains a first polyol, and the component B contains a first component of an isocyanate prepolymer, a second component of acrylate-isocyanate and a third component of acrylate; wherein the component A is 30 to 60 parts by weight with respect to 100 parts by weight of the component B. The polyurethane resin composition and the fiber resin composite material prepared from the polyurethane resin composition are transparent and not easy to yellow, and have excellent comprehensive performances such as heat resistance, alcohol resistance, injection plasticity, curing speed and cost.

Description

Polyurethane resin composition, fiber resin composite material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of polymer preparation, in particular to a polyurethane resin composition, a fiber resin composite material prepared from the polyurethane resin composition and application of the fiber resin composite material.
Background
Resin Transfer Molding (RTM) is a rapid fiber composite forming process that is used extensively in the automotive and aerospace industries. Most of matrix resin of the fiber composite material structural member is epoxy resin, but the matrix resin has the problems of low curing speed, long forming period, easy yellowing, poor light aging performance and the like. Polyurethane resin is mostly adopted as matrix resin in automotive interior, and although the polyurethane resin has excellent characteristics of good transparency, no yellowing and the like, because a large number of intermolecular hydrogen bonds exist in polyurethane, the hydrogen bonds form a highly crosslinked polyurethane network together with physical crosslinking points and chemical crosslinking points, and the hydrogen bonds are easily damaged under a high-temperature condition; when the surface of the polyurethane is contacted with alcohol, alcohol molecules can permeate into the polyurethane network, hydroxyl in the alcohol molecules and carbonyl hydrogen or amino hydrogen in polyurethane hydrogen bonds can form new hydrogen bonds, and the hydrogen bonds of the polyurethane are broken, so that the heat resistance and the alcohol resistance of the polyurethane are poor.
CN106833358A discloses a preparation method of a dual-curing multifunctional urethane acrylate composition: sequentially weighing polymer polyol and photoinitiator, adding the polymer polyol and the photoinitiator into a reaction kettle, and uniformly stirring at room temperature to prepare a solution A; sequentially weighing the reactive diluent, the stabilizer, the oligomer (1) and the oligomer (2) according to the mass ratio of the components, mixing, uniformly stirring to obtain a solution B, and uniformly mixing the solution A and the solution B when in use, thus obtaining the dual-curing multifunctional polyurethane acrylate composition; the oligomer (1) refers to an oligomer obtained by the polyaddition reaction of isocyanate and functional polyol; the oligomer (2) is prepared by performing polyaddition reaction on hydroxyethyl acrylate and isocyanate serving as raw materials.
CN106947053A discloses a preparation method of a modified polyurethane acrylate copolymer, which comprises the following steps: preparing a polyurethane prepolymer: stirring and reacting the isocyanate, the catalyst and the polyether polyol for 1-3h, wherein the molar ratio of the isocyanate to the polyether polyol is 2: 1-1.1:1, and the step two: chain extension: dissolving chain extender carboxyl dihydric alcohol into a solvent, dropwise adding the solution into reaction equipment, and reacting for 2-4h, wherein the molar ratio of the chain extender carboxyl dihydric alcohol to the isocyanate added in the step one is 1: 3-1: 2.1; step three: modification of epoxy resin: adding epoxy resin, and reacting for 2-4h, wherein the molar ratio of the epoxy resin to the chain extender carboxyl dihydric alcohol is 1.5: 1-1: 1; step four: end-capping of hydroxyl-containing acrylates: and (3) dropwise adding a proper amount of hydroxyl-containing acrylate containing a polymerization inhibitor to perform double-bond end-capping reaction, and reacting for 3-5h under the condition of heat preservation, wherein the molar ratio of the hydroxyl-containing acrylate to the isocyanate is 1.8: 1-0.8: 1.
CN104311783A discloses a preparation method of unsaturated hyperbranched polyurethane prepolymer, which is characterized in that the preparation method comprises the following steps: mixing hydroxyl-terminated small molecular polyol and diisocyanate, heating to 80 ℃ for reaction for 2-4 hours, cooling to 40 ℃ after the reaction is finished, adding a terminating agent, heating to 80 ℃ for reaction for 3-5 hours, cooling to 50 ℃ and discharging to obtain unsaturated hyperbranched polyurethane prepolymer; the molecular weight of the unsaturated hyperbranched polyurethane prepolymer is controlled within 3000 g/mol; the molecular weight of the hydroxyl-terminated micromolecular polyol is less than 1000g/mol, and each molecule contains more than two hydroxyl groups; the diisocyanate is one of toluene diisocyanate, 1, 5-naphthalene diisocyanate, 4,4 '-diphenylmethane diisocyanate, 4, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate; the end-capping reagent is one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; the hydroxyl-terminated micromolecule polyol, the diisocyanate and the blocking agent are added according to the weight ratio of 10-15%, 40-55% and 30-45% in sequence.
However, the polyurethane composition of the above-disclosed method is insufficient in overall performance such as injection moldability, curing rate, heat resistance, alcohol resistance and cost, and therefore, it is important to provide a polyurethane composition having good heat resistance, good alcohol resistance, a high curing rate and a low cost.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a polyurethane resin composition, a fiber resin composite material prepared from the polyurethane resin composition and the fiber resin composite material prepared from the polyurethane resin composition, and application of the fiber resin composite material.
In a first aspect, the present invention provides a polyurethane resin composition, which comprises a component a and a component B, wherein the component a comprises a first polyol, and the component B comprises a first component isocyanate prepolymer, a second component acrylate-isocyanate, and a third component acrylate; wherein the component A is 30 to 60 parts by weight with respect to 100 parts by weight of the component B.
Preferably, the first polyol in the a component is a polyether polyol and/or a polyester polyol;
preferably, the first polyol is polyether polyol and polyester polyol, and the amount ratio of the polyester polyol to the polyether polyol is 1: 5-9.
Preferably, the first polyol has a molecular weight of 200-3000 and a functionality of 2-5.
Preferably, the first component: a second component: the dosage ratio of the third component is 1: (0.15-0.35): (0.05-0.15).
Preferably, the first component isocyanate prepolymer is prepared by reacting a first isocyanate with a second polyol.
Preferably, the molar ratio of the second polyol, calculated as hydroxyl groups, to the first isocyanate, calculated as isocyanate groups, is 1: 4-8.
Preferably, the first isocyanate is a non-aromatic isocyanate.
Preferably, the functionality n of the first isocyanate is 2 or more.
Preferably, the non-aromatic isocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate and hydrogenated diphenyl methyl diisocyanate; more preferably isophorone diisocyanate.
Preferably, the second polyol is one or more of a polyether polyol, a polyester polyol and a small molecule polyol.
Preferably, the second polyol is a small molecule polyol with a polyether polyol and/or a polyester polyol.
Preferably, the small molecule polyol is one or more of ethylene glycol, butylene glycol, propylene glycol, glycerol, pentaerythritol and trimethylolpropane.
Preferably, the second component acrylate-isocyanate contains a C ═ C double bond and an isocyanate group.
Preferably, the molecular weight of the second component acrylate-isocyanate is 10000 or less, more preferably 5000 or less.
Preferably, the second component acrylate-isocyanate is blocked by the first hydroxyl group-containing acrylate and/or hydroxyl group-terminated acrylate-urethane resin and the second isocyanate in terms of a molar ratio of hydroxyl groups to isocyanate groups of nOH：nNCO1: 2.5-3.5.
Preferably, the functionality n.gtoreq.2, more preferably 2.5. ltoreq. n.ltoreq.3.5.
Preferably, the second isocyanate is a trimer of hexamethylene diisocyanate.
Preferably, the hydroxyl-terminated acrylate-urethane resin is the reaction product of a second hydroxyl-containing acrylate and a third polyol with a third isocyanate.
Preferably, the third isocyanate is isophorone diisocyanate.
Preferably, the third polyol is a polyether polyol and/or a polyester polyol.
Preferably, the first hydroxyl-containing acrylate is hydroxyethyl methacrylate and/or hydroxypropyl methacrylate.
Preferably, the second hydroxyl-containing acrylate is hydroxyethyl methacrylate and/or hydroxypropyl methacrylate.
Preferably, the third component acrylate is a multifunctional acrylate.
Preferably, the third component acrylate is a trifunctional acrylate.
Preferably, the a component further contains a crosslinking agent in an amount of 8 to 16 parts by weight relative to 100 parts by weight of the first polyol.
Preferably, the a component further contains a photoinitiator, and the photoinitiator is 0.01 to 4 parts by weight with respect to 100 parts by weight of the first polyol.
Preferably, the a component further contains a catalyst in an amount of 0.01 to 4 parts by weight relative to 100 parts by weight of the first polyol.
Preferably, the catalyst is selected from one or more of organometallic catalysts, organoboron catalysts, organic amine catalysts, imidazole catalysts and quaternary ammonium salt catalysts.
Preferably, the crosslinking agent is a multifunctional small molecule crosslinking agent.
Preferably, the multifunctional small molecule cross-linking agent is selected from one or more of trimethylolpropane, glycerol, triethanolamine and diethanolamine.
Preferably, the component A also contains other auxiliary agents, and the other auxiliary agents are selected from one or more of ultraviolet absorbers, antioxidants, light stabilizers, free radical stabilizers, flame retardants and internal mold release agents.
Preferably, the total amount of the other auxiliaries is 0 to 32 parts by weight relative to 100 parts by weight of the first polyol.
Preferably, the molar ratio of the hydroxyl group contained in the a component to the isocyanate group contained in the B component is 1: 0.9-1.4.
Preferably, the A, B components each independently have a viscosity of less than 800mPa · s.
In a second aspect, the present invention provides a method for preparing a fiber resin composite material, wherein the method comprises the following steps:
(1) mixing A, B components of the polyurethane resin composition of the present invention;
(2) and (2) injecting the mixture obtained in the step (1) into a mould paved with a fiber layer, and performing thermosetting molding to obtain the fiber resin composite material.
Preferably, the injection pressure is 10-20 MPa.
Preferably, the conditions for the thermosetting molding include: the heat curing temperature is 60-100 ℃, and the time is 150-450 s.
Preferably, the mold is in a vacuum state, and the vacuum degree in the mold is less than or equal to 500 Pa.
Preferably, the step (2) further comprises subjecting the heat-cured molded article to a UV curing step.
Preferably, the conditions of the UV curing include: the curing energy was 800-.
Preferably, the fibrous layer is made of one or more of carbon fibers, glass fibers, aramid fibers and basalt fibers.
In a third aspect, the invention provides a fiber resin composite material prepared by the method.
In a fourth aspect, the invention provides an application of the polyurethane resin composition or the fiber resin composite material in the preparation of automotive interior parts.
Through the technical scheme, the invention has the following advantages:
(1) in the preparation process, no solvent is used, and the composition and the dosage of the component B are optimized to form an acrylate-polyurethane crosslinking network, so that the polyurethane resin polymer has better heat resistance and alcohol resistance while ensuring certain product rigidity, and meanwhile, the raw material cost is low and the curing speed is high;
(2) the molecular weight, the functionality and the proportion of the components are further optimized, so that the prepared acrylate-polyurethane is transparent and not easy to yellow, has excellent comprehensive performances in injection plasticity, curing speed, heat resistance, alcohol resistance, cost and the like, and can meet the requirements of serving as automobile decorating parts.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides a polyurethane resin composition, wherein the polyurethane resin composition comprises a component A and a component B, the component A comprises a first polyol, and the component B comprises a first component isocyanate prepolymer, a second component acrylate-isocyanate and a third component acrylate; wherein the component A is 30 to 60 parts by weight with respect to 100 parts by weight of the component B.
Preferably, the a component is 35 to 55 parts by weight with respect to 100 parts by weight of the B component.
Preferably, the molar ratio of the hydroxyl group contained in the a component to the isocyanate group contained in the B component is 1: 0.9-1.4. More preferably, the molar ratio of the hydroxyl group contained in the a component to the isocyanate group contained in the B component is 1: 1-1.2; further preferably, the molar ratio of the hydroxyl group contained in the a component to the isocyanate group contained in the B component is 1: 1.03-1.15.
Preferably, the a component and the B component are stored separately.
According to the polyurethane resin composition, an acrylate network structure is introduced into an original polyurethane network structure to form an acrylate-polyurethane dual network structure, and the dual network structure can improve the heat resistance of the resin and prevent alcohol molecules from damaging hydrogen bonds in the polyurethane network, so that the polyurethane resin composition provided by the invention has the advantages of difficult yellowing, good transparency and good heat resistance and alcohol resistance.
Component A
In the present invention, the first polyol of the a component is preferably a polyether polyol and/or a polyester polyol; more preferably, the first polyol is polyether polyol and polyester polyol, and the amount ratio of the polyester polyol to the polyether polyol is 1: 5-9, more preferably 1: 6-8.
In the present invention, there is no particular limitation on the molecular weight of the first polyol in the A component, and preferably, the molecular weight of the first polyol is 200-3000, and the functionality is 2-5; more preferably, the first polyol has a molecular weight of 375-.
Furthermore, the polyether polyol preferably has a molecular weight of 200-2000 and a functionality of 2-5; more preferably, the polyether polyol has a molecular weight of 350-1000 and a functionality of 3-4. Preferably, the polyester polyol has a molecular weight of 800-; more preferably, the polyester polyol has a molecular weight of 1000-.
In the present invention, preferably, the a component further contains a catalyst in an amount of 0.01 to 4 parts by weight relative to 100 parts by weight of the first polyol.
The above catalyst is not particularly limited and may be various catalysts commonly used in the polyurethane industry, and preferably, the catalyst is selected from one or more of organometallic catalysts, organoboron catalysts, organoamine catalysts, imidazole catalysts, and quaternary ammonium salt catalysts.
The organic metal catalyst is not particularly limited, and for example, an organic tin compound, an organic bismuth compound, an organic zinc compound or an organic lead compound, and in the embodiment of the present invention, one or more of dibutyl tin dilaurate, stannous dioctoate and dimethyl tin dineodecanoate are preferable.
In the present invention, preferably, the a component further contains a crosslinking agent in an amount of 8 to 16 parts by weight relative to 100 parts by weight of the first polyol.
The crosslinking agent is not particularly limited, and preferably, the crosslinking agent is a polyfunctional small-molecule crosslinking agent; preferably, the multifunctional small molecule cross-linking agent is selected from one or more of trimethylolpropane, glycerol, triethanolamine and diethanolamine.
In the present invention, preferably, the a component further contains a photoinitiator, and the photoinitiator is 0.01 to 4 parts by weight with respect to 100 parts by weight of the first polyol.
The above photoinitiator is not particularly limited, and preferably, the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide and 4-chlorobenzophenone.
According to the invention, the A component also contains other auxiliary agents, preferably in a total amount of 0 to 32 parts by weight relative to 100 parts by weight of the first polyol.
The above-mentioned other auxiliary agents are not particularly limited, and preferably, the other auxiliary agents are selected from one or more of ultraviolet absorbers, antioxidants, light stabilizers, radical stabilizers, flame retardants, and internal mold release agents. Preferably, the ultraviolet absorber is 0-2 parts by weight, the free radical stabilizer is 0-2 parts by weight, the antioxidant is 0-2 parts by weight, the flame retardant is 0-20 parts by weight, and the internal mold release agent is 0-6 parts by weight, relative to 100 parts by weight of the first polyol.
B component
A first component
According to the present invention, preferably, the first component isocyanate prepolymer is prepared by reacting a first isocyanate with a second polyol. Preferably, the molar ratio of the second polyol, calculated as hydroxyl groups, to the first isocyanate, calculated as isocyanate groups, is 1: 4-8; more preferably, the molar ratio of the second polyol, calculated as hydroxyl groups, to the first isocyanate, calculated as isocyanate groups, is 1: 5-7.
The first isocyanate is not particularly limited, and preferably has a functionality n.gtoreq.2, and more preferably n is 2 to 2.5. Further, the first isocyanate is preferably a non-aromatic isocyanate. The non-aromatic isocyanate is preferably selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate and hydrogenated diphenyl methyl diisocyanate; more preferably, the non-aromatic isocyanate is isophorone diisocyanate.
In the present invention, the second polyol is not particularly limited, and preferably, the second polyol is one or more of polyether polyol, polyester polyol and small molecule polyol; more preferably, the second polyol is a small molecule polyol with a polyether polyol and/or a polyester polyol; further preferably, the small molecule polyol is one or more of ethylene glycol, butylene glycol, propylene glycol, glycerol, pentaerythritol and trimethylolpropane.
Preferably, the polyether polyol has a molecular weight of 200-2000 and a functionality of 2-5; more preferably, the polyether polyol has a molecular weight of 400-.
Preferably, the polyester polyol has a molecular weight of 800-; more preferably, the polyester polyol has a molecular weight of 1000-.
In a preferred embodiment of the present invention, the first component isocyanate prepolymer is prepared by reacting the non-aromatic isocyanate with a polyether polyol and/or a polyester polyol and trimethylolpropane, wherein the polyether polyol and/or the polyester polyol is 12 to 15 parts by weight and the trimethylolpropane is 4 to 6 parts by weight based on 100 parts by weight of the non-aromatic isocyanate.
A second component
According to the invention, the second component acrylate isocyanate contains a C ═ C double bond and isocyanate groups. Preferably, the molecular weight of the second component acrylate-isocyanate is less than or equal to 10000, more preferably, the molecular weight of the second component acrylate-isocyanate is less than or equal to 5000; further preferably, the molecular weight of the second component acrylate-isocyanate is 500-. Preferably, the second component acrylate-isocyanate is blocked by the first hydroxyl group-containing acrylate and/or hydroxyl group-terminated acrylate-urethane resin and the second isocyanate in terms of a molar ratio of hydroxyl groups to isocyanate groups of nOH：nNCO1: 2.5-3.5.
According to the present invention, preferably, the first hydroxyl group-containing acrylate is hydroxyethyl methacrylate and/or hydroxypropyl methacrylate.
According to the invention, the functionality n.gtoreq.2, preferably 2.5. ltoreq. n.ltoreq.3.5, of the second isocyanate is preferred. The n may be, for example, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, or the like.
In a particularly preferred embodiment of the invention, the second isocyanate is a trimer of hexamethylene diisocyanate.
According to the present invention, preferably, the hydroxyl-terminated acrylate-urethane resin is the product of the reaction of a second hydroxyl-containing acrylate and a third polyol with a third isocyanate. Specifically, the hydroxyl-terminated acrylate-urethane resin may be a second hydroxyl-containing acrylate and a third polyol to a third isocyanate in a molar ratio of 1: 1:1 product of the reaction.
In the present invention, the third polyol is not particularly limited, and preferably the third polyol is a polyether polyol and/or a polyester polyol.
Preferably, the polyether polyol has a molecular weight of 200-2000 and a functionality of 2-5; more preferably, the polyether polyol has a molecular weight of 400-1000 and a functionality of 3-4.
Preferably, the polyester polyol has a molecular weight of 800-; more preferably, the polyester polyol has a molecular weight of 1000-.
According to the present invention, preferably, the third isocyanate is a diisocyanate; more preferably, the third isocyanate is one or more of isophorone diisocyanate (IPDI), hydrogenated diphenylmethyl diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), and cyclohexyl diisocyanate.
In a particularly preferred embodiment of the present invention, the third isocyanate is isophorone diisocyanate.
According to the present invention, preferably, the second hydroxyl group-containing acrylate is hydroxyethyl methacrylate and/or hydroxypropyl methacrylate.
According to the present invention, preferably, the reaction of the first hydroxyl-containing acrylate and/or hydroxyl-terminated acrylate-urethane resin with the second isocyanate is carried out in the presence of a catalyst, which may be, for example, one or more of dibutyltin dilaurate, stannous dioctoate, and dimethyltin dineodecanoate.
Preferably, the catalyst is added in an amount of 0.005 to 0.02 parts by weight, more preferably 0.01 to 0.02 parts by weight, relative to 100 parts by weight of the second isocyanate.
Third component
According to the present invention, preferably, the third component acrylate is a multifunctional acrylate; further preferably, the third component acrylate is a trifunctional acrylate; more preferably, the trifunctional acrylate is one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate. The third component acrylate can play a role in diluting in the polyurethane resin composition, and can generate a crosslinking reaction with the second component acrylate-isocyanate acrylate or the third component acrylate, so that the crosslinking degree of the polymer is improved, and the heat resistance and the alcohol resistance of the prepared polyurethane resin are further improved.
According to the present invention, preferably, the first component: a second component: the dosage ratio of the third component is 1: (0.15-0.35): (0.05-0.15), more preferably 1: (0.2-0.3): (0.06-0.12), more preferably 1: (0.26-0.28): (0.09-0.1). In a particular embodiment of the invention, the ratio of the amounts is 1: 0.274: 0.096.
according to the present invention, preferably, the first component, the second component and the third component are stored separately.
In a second aspect, the present invention provides a method for preparing a fiber resin composite material, wherein the method comprises the following steps:
(1) mixing A, B components of the polyurethane resin composition of the present invention; (2) and (2) injecting the mixture obtained in the step (1) into a mould paved with a fiber layer, and performing thermosetting molding to obtain the fiber resin composite material.
According to the method provided by the invention, through thermosetting molding, NCO groups in the second component of acrylate-isocyanate react with hydroxyl groups in the first polyol, so that the molecules of the second component of acrylate-isocyanate completely enter a polyurethane network main chain, the strength and rigidity of a molded body are ensured, and the molded body is not easy to deform while demolding is ensured.
According to the method of the present invention, preferably, in the step (1), the B component is mixed in advance and then mixed with the A component.
According to the method of the present invention, preferably, the ratio of the number of moles of hydroxyl groups contained in the a component to the number of moles of isocyanate groups contained in the B component is 1: the B component and the A component are used in a manner of 0.9-1.4; more preferably, the ratio of the number of moles of hydroxyl groups contained in the a component to the number of moles of isocyanate groups contained in the B component is 1: 1-1.2 using component B and component A; further preferably, the ratio of the number of moles of hydroxyl groups contained in the a component to the number of moles of isocyanate groups contained in the B component is 1: the B component and the A component are used in a manner of 1.03 to 1.15.
According to the method of the present invention, preferably, the a component is 35 to 55 parts by weight with respect to 100 parts by weight of the B component. By mixing the component B and the component A in the above range, the above ratio of the number of moles of the isocyanate group and the hydroxyl group can be satisfied.
According to the method of the present invention, preferably, the reaction solution in step (1) is injected into the mold in which the fiber layer is laid, by a high-pressure injection machine. Preferably, the injection pressure is 10-20MPa, more preferably 12-15 MPa.
According to the method of the present invention, preferably, the conditions of the thermosetting molding include: the heat curing temperature is 60-100 ℃, and the time is 150-450 s.
Preferably, the mould is in a vacuum state, and the vacuum degree in the mould is less than or equal to 500Pa, and more preferably, the vacuum degree is less than or equal to 300 Pa.
Preferably, the temperature of the reaction feed liquid in the step (2) is 30-60 ℃, more preferably, the temperature of the reaction feed liquid in the step (2) is 40-60 ℃, and the temperature of the die is 70-100 ℃.
In the method of the present invention, preferably, the step (2) further comprises subjecting the molded article taken out by the heat curing to a UV curing step; more preferably, the conditions of the UV curing include: the curing energy was 800-.
According to the method of the present invention, preferably, the fiber layer is made of one or more of carbon fiber, glass fiber, aramid fiber and basalt fiber. Preferably, in the method of the present invention, the fiber layer is preferably carbon fiber, and the carbon fiber may have a specification of 1K, 3K, 6K, 12K, 24K, and more preferably 3K carbon fiber woven by plain weave, twill weave, satin weave, or unidirectional cloth.
The thickness of the fiber layer is not particularly limited, but is preferably 0.1 to 1.5mm, more preferably 0.2 to 0.5 m.
In order to further improve the mixing efficiency and the wettability to the fiber layer, the viscosity of the A, B components in the polyurethane resin composition is preferably each independently less than 800mPa · s, more preferably less than 500mPa · s, and even more preferably less than 300mPa · s.
In a third aspect, the invention provides a fiber resin composite material prepared by the method.
Preferably, the resin content in the fiber resin composite is greater than 50% by weight.
Preferably, the thickness of the fiber resin composite material is 0.3 to 1.8mm, more preferably 0.8 to 1.5 mm.
In the specific embodiment of the invention, the prepared carbon fiber resin composite material is transparent, and the hardness of the carbon fiber resin composite material at 25 ℃ is greater than Shore 80D, and the hardness of the carbon fiber resin composite material at 100 ℃ is greater than 70D.
In a fourth aspect, the invention provides an application of the polyurethane resin composition or the fiber resin composite material in the preparation of automotive interior parts.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
The test method comprises the following steps:
hardness: the measurement was carried out using a Shore hardness tester.
Alcohol resistance: 0.1ml of alcohol is dripped on the surface of the sample, the sample is placed and observed at room temperature, and when no obvious trace is left on the surface of the sample, the sample is defined as pass, namely the sample has alcohol resistance; when the sample surface showed a clear mark, it was defined as fail, i.e. it had no alcohol resistance.
Synthesis of component B
B-1：
A first component:
placing 3 parts by weight of trimethylolpropane and 8 parts by weight of adipic acid polyester polyol (purchased from Shandonghua Daichemical group Co., Ltd., model 255, trifunctional group, molecular weight 2500, hydroxyl value 162.5mgKOH/g) into a three-neck flask, vacuumizing at 110 ℃, removing water for 1 hour, cooling to 90 ℃, slowly adding 62 parts by weight of isophorone diisocyanate (IPDI) under the protection of nitrogen, stirring at constant temperature for 5 hours until the content of NCO is not changed any more, wherein the content of NCO is as follows: 27.7 percent.
A second component:
adding 31.08 parts by weight of isophorone diisocyanate and 18.2 parts by weight of hydroxyethyl methacrylate into a reactor, uniformly stirring, and reacting at 65 ℃ until the NCO value is constant; 144.06 parts by weight of a dry polyether polyol (DL1000, available from Dow of Lanxingdong Co., Ltd., molecular weight 1000, hydroxyl value 112mg KOH/g), 0.01 part by weight of dibutyltin dilaurate (T12) were added and the reaction was stirred until the NCO value became constant; 76.7 parts by weight of a trimer of hexamethylene diisocyanate (available from Wanhua chemical Co., Ltd., type HT-600, the same applies hereinafter) were added thereto, and the reaction was continued with stirring until the NCO value became constant and the NCO content thereof was 4.3%.
B-1 resin Synthesis: 73 parts of the first component, 20 parts of the second component and 7 parts of trimethylolpropane triacrylate are taken and stirred uniformly, and the NCO content is 21%.
B-2：
A first component: the first component of the same B-1.
A second component:
adding 31.08 parts by weight of isophorone diisocyanate and 18.2 parts by weight of hydroxyethyl methacrylate into a reactor, uniformly stirring, and reacting at 65 ℃ until the NCO value is constant; 57.62 parts by weight of a dry polyether polyol (DL400, from Dow, N.C., having a molecular weight of 400 and a hydroxyl value of 280mg KOH/g), 0.01 part by weight of dibutyltin dilaurate (T12) were added and the reaction was continued with stirring until the NCO value became constant; 76.7 parts by weight of a trimer of hexamethylene diisocyanate were added, and the reaction was continued with stirring until the NCO value became constant, the NCO content of which was 6.3%.
B-2 resin Synthesis: 73 parts of the first component, 20 parts of the second component and 7 parts of trimethylolpropane triacrylate are taken and stirred uniformly, and the NCO content is 21.4%.
B-3：
A first component: the first component of the same B-1.
A second component:
adding 31.08 parts by weight of isophorone diisocyanate and 18.2 parts by weight of hydroxyethyl methacrylate into a reactor, uniformly stirring, and reacting at 65 ℃ until the NCO value is constant; 144.06 parts by weight of a dry polycaprolactone polyol (molecular weight 1000, hydroxyl number 112mg KOH/g, from Wailawa industries Ltd.) and 0.01 part by weight of dibutyltin dilaurate (T12) were added and the reaction was continued with stirring until the NCO value became constant; 76.7 parts by weight of a trimer of hexamethylene diisocyanate were added, and the reaction was continued with stirring until the NCO value became constant, the NCO content of which was 4.3%.
B-3 resin Synthesis: 73 parts of the first component, 20 parts of the second component and 7 parts of trimethylolpropane triacrylate are taken and stirred uniformly, and the NCO content is 21%.
B-4：
A first component: the first component of the same B-1.
A second component:
adding 18.2 parts by weight of hydroxyethyl methacrylate into the reactor, continuing to add 0.01 part by weight of dibutyltin dilaurate (T12), and continuing to react with stirring until the NCO value is constant; 76.7 parts by weight of a trimer of hexamethylene diisocyanate were added, and the reaction was continued with stirring until the NCO value became constant, the NCO content of which was 12.3%.
B-4 resin Synthesis: 73 parts of the first component, 20 parts of the second component and 7 parts of trimethylolpropane triacrylate are taken and stirred uniformly, and the NCO content is 22.6%.
B-5
A first component: the first component of the same B-1.
A second component: adding 31.08 parts by weight of isophorone diisocyanate and 18.2 parts by weight of hydroxyethyl methacrylate into a reactor, uniformly stirring, and reacting at 65 ℃ until the NCO value is constant; 144.06 parts by weight of a dry polyether polyol (DL1000, molecular weight 1000, hydroxyl value 112mgKOH/g, from Dow-Town Ltd., Bluestar) and 0.01 part by weight of dibutyltin dilaurate (T12) were added and the reaction was continued with stirring until the NCO value became constant; 67.23 parts by weight of a trimer of hexamethylene diisocyanate were added and the reaction was continued with stirring until the NCO value became constant and the NCO content thereof was 3.5%.
B-5 resin Synthesis: 73 parts of the first component, 20 parts of the second component and 7 parts of trimethylolpropane triacrylate are taken and stirred uniformly, and the NCO content is 20.9%.
B-6
A first component: the first component of the same B-1.
A second component: adding 31.08 parts by weight of isophorone diisocyanate and 18.2 parts by weight of hydroxyethyl methacrylate into a reactor, uniformly stirring, and reacting at 65 ℃ until the NCO value is constant; 144.06 parts by weight of a dry polyether polyol (DL1000, molecular weight 1000, hydroxyl value 112mgKOH/g, from Dow-Town Ltd., Bluestar) and 0.01 part by weight of dibutyltin dilaurate (T12) were added and the reaction was continued with stirring until the NCO value became constant; 94.12 parts by weight of a trimer of hexamethylene diisocyanate (HT-600, from Waals) were added and the reaction was continued with stirring until the NCO value became constant and the NCO content was 5.3%. .
B-6 resin Synthesis: 73 parts of the first component, 20 parts of the second component and 7 parts of trimethylolpropane triacrylate are taken and stirred uniformly, and the NCO content is 21.2%.
B-7：
Placing 4 parts by weight of trimethylolpropane and 12 parts by weight of adipic acid polyester polyol (which is purchased from Shandong Hua Daichou chemical group Co., Ltd., model number is 255, three functional groups, molecular weight is 2500, and hydroxyl value is 162.5mgKOH/g) into a three-neck flask, vacuumizing at 110 ℃, removing water for 1 hour, cooling to 90 ℃, slowly adding 84 parts by weight of isophorone diisocyanate (IPDI) under the protection of nitrogen, stirring at constant temperature for 5 hours, and reacting until the content of NCO is not changed, wherein the content of NCO is as follows: 27.4 percent.
Examples 1 to 6
A, B two components were mixed so that the isocyanate index was 1.05 (isocyanate group) according to the results shown in Table 1, A, B two components were injected into a closed mold in which a carbon fiber cloth (3K, thickness 0.2mm) was previously laid by a high pressure injection machine (injection pressure 12MPa) and evacuated (degree of vacuum 200Pa), thermosetting molding (mold temperature 90 ℃, material temperature 60 ℃ and demolding time 300s) was performed, the molded article was taken out, and UV curing (energy 1000J) was performed to produce a carbon fiber resin composite material, and the test results are shown in Table 1.
Comparative example 1
The same preparation method as in example 1 was used except that no UV curing was performed, and the test results are shown in table 1.
TABLE 1
Figure BDA0001831036360000171
Figure BDA0001831036360000181
Note: polyol 1 (trifunctional polyether polyol, hydroxyl value 450mg KOH/g) was purchased from Dow corporation, Lanxingdong, Inc. model number 450, molecular weight 375; polyol 2 (trifunctional polyester polyol) was purchased from Shandonghua Daichi chemical group, Inc. with a model number of 255, a molecular weight of 2500, and a hydroxyl value of 162.5 mgKOH/g; the light stabilizer is purchased from Ciba extract, and the model is Tian Lai Zheng 292 and Tian Lai Zheng 1130; the antioxidant was model number 1135R.
As can be seen by comparing examples 1 to 6 in Table 1 with comparative example 1, the two-component polyurethane composition of the present invention has good injection moldability, curing speed, heat resistance, and alcohol resistance, and can satisfy the requirements as automotive trims.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (16)

1. The polyurethane resin composition is characterized by comprising a component A and a component B, wherein the component A contains a first polyol, and the component B contains a first component isocyanate prepolymer, a second component acrylate-isocyanate and a third component acrylate;
wherein the component A is 30 to 60 parts by weight with respect to 100 parts by weight of the component B.
2. The polyurethane resin composition according to claim 1, wherein the first polyol in the a-component is a polyether polyol and/or a polyester polyol;
preferably, the first polyol is polyether polyol and polyester polyol, and the amount ratio of the polyester polyol to the polyether polyol is 1: 5-9;
preferably, the first polyol has a molecular weight of 200-3000 and a functionality of 2-5.
3. The polyurethane resin composition according to claim 1 or 2, wherein the first component: a second component: the dosage ratio of the third component is 1: (0.15-0.35): (0.05-0.15).
4. The polyurethane resin composition according to claim 1 or 2, wherein the first component isocyanate prepolymer is prepared by reacting a first isocyanate with a second polyol;
preferably, the molar ratio of the second polyol, calculated as hydroxyl groups, to the first isocyanate, calculated as isocyanate groups, is 1: 4-8;
preferably, the first isocyanate is a non-aromatic isocyanate;
preferably, the functionality n of the first isocyanate is not less than 2;
preferably, the non-aromatic isocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate and hydrogenated diphenyl methyl diisocyanate; more preferably isophorone diisocyanate;
preferably, the second polyol is one or more of a polyether polyol, a polyester polyol and a small molecule polyol;
preferably, the second polyol is a small molecule polyol and a polyether polyol and/or a polyester polyol;
preferably, the small molecule polyol is one or more of ethylene glycol, butylene glycol, propylene glycol, glycerol, pentaerythritol and trimethylolpropane.
5. The polyurethane resin composition according to claim 4, wherein the second component acrylate-isocyanate contains a C ═ C double bond and an isocyanate group;
preferably, the molecular weight of the second component acrylate-isocyanate is less than or equal to 10000, more preferably, the molecular weight of the second component acrylate-isocyanate is less than or equal to 5000;
preferably, the second component acrylate-isocyanate is blocked by the first hydroxyl group-containing acrylate and/or hydroxyl group-terminated acrylate-urethane resin and the second isocyanate in terms of a molar ratio of hydroxyl groups to isocyanate groups of nOH：nNCO1: 2.5-3.5;
preferably, the functionality n of the second isocyanate is 2 or more, more preferably 2.5 or less and n is 3.5 or less;
preferably, the second isocyanate is a trimer of hexamethylene diisocyanate;
preferably, the hydroxyl-terminated acrylate-urethane resin is the reaction product of a second hydroxyl-containing acrylate and a third polyol with a third isocyanate;
preferably, the third isocyanate is isophorone diisocyanate;
preferably, the third polyol is a polyether polyol and/or a polyester polyol;
preferably, the first hydroxyl-containing acrylate is hydroxyethyl methacrylate and/or hydroxypropyl methacrylate;
preferably, the second hydroxyl-containing acrylate is hydroxyethyl methacrylate and/or hydroxypropyl methacrylate;
preferably, the third component acrylate is a multifunctional acrylate;
preferably, the third component acrylate is a trifunctional acrylate.
6. The polyurethane resin composition according to claim 1, wherein the a-side further contains a crosslinking agent in an amount of 8 to 16 parts by weight relative to 100 parts by weight of the first polyol;
preferably, the a component further contains a photoinitiator, the photoinitiator being 0.01 to 4 parts by weight relative to 100 parts by weight of the first polyol;
preferably, the a component further contains a catalyst in an amount of 0.01 to 4 parts by weight relative to 100 parts by weight of the first polyol.
7. The polyurethane resin composition according to claim 6, wherein the catalyst is selected from one or more of organometallic catalysts, organoboron catalysts, organoamine catalysts, imidazole catalysts, and quaternary ammonium salt catalysts;
preferably, the crosslinking agent is a multifunctional small molecule crosslinking agent;
preferably, the multifunctional small molecule cross-linking agent is selected from one or more of trimethylolpropane, glycerol, triethanolamine and diethanolamine.
8. The polyurethane resin composition according to claim 7, wherein the A-side further contains other auxiliaries selected from one or more of ultraviolet absorbers, antioxidants, light stabilizers, radical stabilizers, flame retardants, and internal mold release agents;
preferably, the total amount of the other auxiliaries is 0 to 32 parts by weight relative to 100 parts by weight of the first polyol.
9. The polyurethane resin composition according to any one of claims 1 to 8, wherein a molar ratio of the hydroxyl group contained in the A component to the isocyanate group contained in the B component is 1: 0.9-1.4.
10. The polyurethane resin composition of any of claims 1-8, wherein the A, B components each independently have a viscosity of less than 800 mPa-s.
11. The preparation method of the fiber resin composite material is characterized by comprising the following steps:
(1) mixing A, B components of the polyurethane resin composition according to any one of claims 1 to 10;
(2) and (2) injecting the mixture obtained in the step (1) into a mould paved with a fiber layer, and performing thermosetting molding to obtain the fiber resin composite material.
12. The production method according to claim 11, wherein the pressure of the injection is 10-20 MPa;
preferably, the conditions for the thermosetting molding include: the heat curing temperature is 60-100 ℃, and the time is 150-450 s;
preferably, the mold is in a vacuum state, and the vacuum degree in the mold is less than or equal to 500 Pa.
13. The production method according to claim 11, wherein the step (2) further comprises subjecting the heat-cured molded article to a UV curing step;
preferably, the conditions of the UV curing include: the curing energy was 800-.
14. The production method according to claim 11, wherein the fiber layer is made of one or more of carbon fiber, glass fiber, aramid fiber, and basalt fiber.
15. A fibre resin composite material prepared by the method of any one of claims 11 to 14.
16. Use of the polyurethane resin composition of any one of claims 1 to 10 or the fiber resin composite of claim 15 for the preparation of automotive interior parts.
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